CN112403520A - Preparation and application of vermiculite supported phosphotungstic acid green catalyst - Google Patents

Preparation and application of vermiculite supported phosphotungstic acid green catalyst Download PDF

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CN112403520A
CN112403520A CN201910779525.2A CN201910779525A CN112403520A CN 112403520 A CN112403520 A CN 112403520A CN 201910779525 A CN201910779525 A CN 201910779525A CN 112403520 A CN112403520 A CN 112403520A
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vermiculite
catalyst
phosphotungstic acid
acid
preparation
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巩建军
薛来奇
刘颖
宋武林
董庆孟
曹江风
田舟琪
洪亮
张萌
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CHANGJI UNIVERSITY
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/30Tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method and application of a vermiculite supported phosphotungstic acid green catalyst, wherein phosphotungstic acid is used as an active species, high-temperature roasted sulfuric acid modified vermiculite is used as a carrier, one of sodium hexametaphosphate, sodium phosphate and sodium silicate is used as a binder to prepare the phosphotungstic acid supported catalyst, the phosphotungstic acid supported catalyst is applied to research of a heterogeneous reaction system for preparing cyclohexene by dehydrating cyclohexanol, when the binder dosage is 0.3 g, the phosphotungstic acid is 0.6 g, the modified vermiculite is 1 g, and the catalyst dosage is 0.6 g, the cyclohexene selectivity is 100%, the yield reaches 93.70%, the catalyst can be recycled after the reaction is finished, and the catalyst still has high yield after being reused for 8 times.

Description

Preparation and application of vermiculite supported phosphotungstic acid green catalyst
Technical Field
The invention relates to a preparation method and application of a vermiculite supported phosphotungstic acid green catalyst, and belongs to the technical field of chemical industry.
Background
Cyclohexene as an important organic chemical intermediate raw material is commonly used for synthesizing pesticides, medicines and high polymers, is used for preparing catalysts and solvents in chemical production, and is used as an extracting agent and a high-survival-value stabilizer in the petroleum industry, and has large demand and wide application. In the conventional industrial production of cyclohexene cyclohexanol is usually prepared by liquid phase dehydration of cyclohexanol using concentrated sulfuric acid as catalyst. Concentrated sulfuric acid as a catalyst has the defects of equipment corrosion, serious carbonization, low yield (70 percent), environmental pollution, difficult catalyst recycling and the like. With the introduction of the concept of "green chemistry" and the improvement of environmental protection in recent years, it has become necessary to seek to develop a novel green heterogeneous recyclable catalyst.
Recent research at home and abroad shows that the heteropoly acid has a determined structure, simultaneously has acidity and oxidizability, can be used as an acid-base, redox or bifunctional catalyst, and can systematically regulate and control the performance of the catalyst by selecting constituent elements (coordination atoms, central atoms, counter ions and the like) under the condition of not changing the structure of heteropolyanions. In solid phase catalytic reactions, polar molecules can enter the catalyst bulk phase, with a "pseudo-liquid phase" behavior that makes the entire bulk phase a reaction field. Therefore, the catalyst has the characteristics of high activity, good selectivity, slight corrosion, mild reaction conditions and the like.
Phosphotungstic acid (H)3PW12O40·nH2O) oxygen-containing polyacid which is formed by coordination bridging of heteroatom P and coordination atom W through oxygen atoms in a certain structure has a Keggin structure, has both acid catalysis and oxidation catalysis functions, is protonic acid with uniform strength, and has high catalytic activity. Due to the poleThe catalyst is easy to dissolve in polar solvent and is difficult to be used as a solid acid catalyst in a polar reaction system, and the defects of easy sintering at high temperature, easy carbon deposition and inactivation on the surface, uneven acid strength distribution and the like exist, so that the industrial application of the catalyst is limited. In order to overcome the above-mentioned drawbacks, it is generally carried on a suitable carrier to increase the specific surface area and to improve the dispersion of the active ingredient. The common carriers comprise alumina, silica gel, silica, activated carbon, diatomite, montmorillonite and the like, and compared with the carriers, the vermiculite has the characteristics of large crystal grain, easiness in expansion, high temperature resistance, large specific surface area and the like, but the expanded vermiculite is rarely reported as the carrier.
The vermiculite is a layered silicate mineral with a 2:1 type structural layer, and water molecules and exchangeable cations are arranged in interlayer domains. When high-temperature roasting is carried out, water molecules between layers are heated and gasified to generate pressure, so that the structure is quickly expanded, and the volume is accelerated to expand to form the expanded vermiculite. The vermiculite has rich negative charges between layers, and the main reason for the generation is Al existing in tetrahedral gaps in the structure3+、Fe3+Substituting for Si4+And the vermiculite structural layer is charged with redundant negative charges. In addition, part of water molecules between layers surround cations between layers to form coordination octahedrons, and occupy specific positions in the structure, and part of water molecules are in a free state. The structural characteristics enable the vermiculite to have stronger adsorption performance and cation exchange capacity, and is an excellent green catalyst carrier. The vermiculite modified by the sulfuric acid can dissolve out pore particle impurities and increase the specific surface area through ion exchange, and can form broken bonds of-Al-OH, -Si-OH and the like with Bronsted activity, and the broken bonds have strong adsorption performance and are favorable for strong adsorption of active components.
Disclosure of Invention
The invention aims to overcome the defects that the catalyst is difficult to separate, the equipment is corroded, the environment is polluted and the like in the traditional preparation process of cyclohexene, and provides a vermiculite supported phosphotungstic acid green catalyst which is convenient to recycle.
In order to achieve the purpose, the invention provides the following technical scheme: the catalyst takes vermiculite as a carrier, takes one of sodium hexametaphosphate, sodium phosphate and sodium silicate as a binder, and the phosphotungstic acid is loaded on the carrier to form the solid heteropoly acid catalyst, wherein the loading capacity of the phosphotungstic acid is 20-80%.
Preferably, the carrier vermiculite is high-temperature roasted expanded vermiculite (200-1000 ℃) and the Cation Exchange Capacity (CEC) of the carrier vermiculite is 0.998 mmol/g.
Preferably, the cation exchange modification treatment is carried out by using 2 mol/L sulfuric acid before use.
Preferably, the preparation method of the vermiculite supported phosphotungstic acid green catalyst comprises the following steps: (1) dissolving 0.1-0.5 g of binder in 2 mol/L of one of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and oxalic acid, wherein the dosage of the binder is 10 ml, and then stirring for 10 min at room temperature by magnetic force until the binder is completely dissolved;
(2) adding 1 g of the high-temperature roasted modified vermiculite powder as shown in the claim 2 into the acid solution obtained in the step (1), and stirring for 1 hour at room temperature to uniformly mix the powder;
(3) dissolving 0.2-0.8 g of phosphotungstic acid in 5 ml of deionized water, adding the mixture obtained in the step (2) after complete dissolution, and stirring in an oil bath at 80 ℃ for 12 hours;
(4) stirring the mixed solution obtained in the step (3) in a water bath at 100 ℃ and evaporating to dryness, and then drying in an oven at 100 ℃ for 6 hours;
(5) and (4) roasting the powder obtained in the step (4) in a muffle furnace at 200 ℃ for 4 h to obtain the phosphotungstic acid supported catalyst.
Preferably, the high-temperature roasted vermiculite used in the step (2) is 80 meshes and is produced in Yuli county in Xinjiang.
Preferably, 0.4 to 1 g of the catalyst prepared in the claim 4 is placed in a single-neck flask with a fractionating column and a thermometer, 10 ml of cyclohexanol is added and stirred uniformly at room temperature, the mixture is stirred in an oil bath at 180 ℃ for reaction, a distillate is collected to separate a water layer, anhydrous calcium chloride is used for removing moisture of an organic layer, and a fraction at 80 to 85 ℃ is collected by atmospheric distillation to obtain a colorless and transparent cyclohexene product with pungent smell.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional catalyst concentrated sulfuric acid, the catalyst has higher catalytic activity, the highest yield is 93.70 percent, and the dosage of the catalyst is 0.6 g.
2. The prepared catalyst is a solid supported catalyst, is applied to a heterogeneous reaction system, and is easy to separate and purify and reuse after the reaction is finished.
3. The prepared catalyst loaded active component is phosphotungstic acid, has small influence on equipment and environment, and is a green and environment-friendly catalyst.
4. The carrier vermiculite has larger crystal grains and specific surface area and is high-temperature resistant, so that the supported catalyst has high-temperature sintering resistance.
5. The vermiculite carrier has cation exchange performance, so that the surface of the carrier modified by sulfuric acid has broken bonds of-Al-OH, -Si-OH and the like with Bronst activity, has strong adsorption effect on active components, and improves the stability of the catalyst.
6. The phosphotungstic acid supported catalyst active component prepared by the over-volume impregnation method has higher dispersity, so that the loss of the active component and high-temperature sintering are weakened.
7. The binder is introduced in the preparation process of the catalyst, so that the problem of low load capacity only depending on the adsorption effect of the catalyst carrier is solved.
Detailed Description
The technical solution of the present invention will be clearly and completely described with reference to the following specific examples. The described embodiments are only some embodiments of the present invention, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
The invention provides a technical scheme that: the catalyst takes vermiculite as a carrier, takes one of sodium hexametaphosphate, sodium phosphate and sodium silicate as a binder, and the phosphotungstic acid is loaded on the carrier to form the solid heteropoly acid catalyst, wherein the loading capacity of the phosphotungstic acid is 20-80%.
The carrier vermiculite is high-temperature roasted expanded vermiculite (200-1000 ℃), and the Cation Exchange Capacity (CEC) of the carrier vermiculite is 0.998 mmol/g.
Before use, the cation exchange modification treatment is carried out by using 2 mol/L sulfuric acid.
The preparation method of the vermiculite supported phosphotungstic acid green catalyst comprises the following steps:
(1) dissolving 0.1-0.5 g of binder in 2 mol/L of one of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and oxalic acid, wherein the dosage of the binder is 10 ml, and then stirring for 10 min at room temperature by magnetic force until the binder is completely dissolved;
(2) adding 1 g of the high-temperature roasted modified vermiculite powder as shown in the claim 2 into the acid solution obtained in the step (1), and stirring for 1 hour at room temperature to uniformly mix the powder;
(3) dissolving 0.2-0.8 g of phosphotungstic acid in 5 ml of deionized water, adding the mixture obtained in the step (2) after complete dissolution, and stirring in an oil bath at 80 ℃ for 12 hours;
(4) stirring the mixed solution obtained in the step (3) in a water bath at 100 ℃ and evaporating to dryness, and then drying in an oven at 100 ℃ for 6 hours;
(5) and (4) roasting the powder obtained in the step (4) in a muffle furnace at 200 ℃ for 4 h to obtain the phosphotungstic acid supported catalyst.
The high-temperature roasted vermiculite used in the step (2) is 80 meshes and is produced in Yuli county in Xinjiang.
Placing 0.4-1 g of the catalyst prepared in the claim 4 into a single-neck flask with a fractionating column and a thermometer, adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃, collecting a distillate, separating a water layer, removing water in an organic layer by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by atmospheric distillation to obtain a colorless and transparent cyclohexene product with pungent smell.
Example 1
Preparation of the catalyst with a quantity of binder (AD) of 0.1 g: dissolving 0.1 g of binder in 2 mol/L acid, wherein the dosage is 10 ml, stirring at room temperature by magnetic force for 10 min until the binder is completely dissolved, adding 1 g of high-temperature roasted vermiculite powder, stirring at room temperature for 1h to mix the vermiculite powder uniformly, adding a phosphotungstic acid solution (0.6 g of phosphotungstic acid is dissolved in 5 ml of deionized water) prepared in advance, stirring in an oil bath at 80 ℃ for 12 h, then placing the mixture in a water bath at 100 ℃, stirring and evaporating to dryness, drying in an oven at 100 ℃ for 6 h, and roasting in a muffle furnace at 200 ℃ for 4 h to obtain a phosphotungstic acid supported catalyst PW, wherein the mark is 0.6-0.1AD/1 aEVM.
Example 2
Preparation of catalyst with binder amount of 0.2 g: wherein the binder was 0.2 g, and the other steps were as described in example 1 and labeled PW0.6-0.2AD/1 aEVM.
Example 3
Preparation of catalyst with binder amount of 0.3 g: wherein the binder was 0.3 g, and the other steps were as described in example 1 and labeled PW0.6-0.3AD/1 aEVM.
Example 4
Preparation of catalyst with binder amount of 0.4 g: the binder was 0.4g, and the other steps were as described in example 1 and labeled PW0.6-0.4AD/1 aEVM.
Example 5
Preparation of catalyst with binder amount of 0.5 g: wherein the binder was 0.5 g, and the other steps are as described in example 1 and labeled PW0.6-0.5AD/1 aEVM.
Examples 6 to 10
Experiment of the effect of different amounts of binder on catalytic activity: the catalytic activity of the supported catalysts with different AD contents prepared in examples 1 to 5 on the dehydration reaction of cyclohexanol was evaluated by the following method.
Putting 0.6 g of the prepared catalyst into a single-neck flask with a fractionating column and a thermometer, adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃, collecting a distillate, separating a water layer, removing a plurality of layers of water by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by normal pressure distillation to obtain a colorless and transparent cyclohexene product with pungent smell, wherein the specific cyclohexene yield is shown in table 1.
TABLE 1 Effect of different AD on cyclohexene Selectivity and yield
Sample (I) Cyclohexene selectivity (%) Cyclohexene yield (%)
PW0.6-0.1AD/1aEVM 100 72.77
PW0.6-0.2AD/1aEVM 100 80.58
PW0.6-0.3AD/1aEVM 100 93.70
PW0.6-0.4AD/1aEVM 100 85.44
PW0.6-0.5AD/1aEVM 100 75.32
Example 11
The preparation method of the catalyst with the phosphotungstic acid loading of 0.2 g comprises the following steps: dissolving 0.3 g of AD in 2 mol/L acid, wherein the dosage is 10 ml, stirring at room temperature by magnetic force for 10 min until the AD is completely dissolved, adding 1 g of high-temperature roasted vermiculite powder, stirring at room temperature for 1h to mix uniformly, then adding a phosphotungstic acid solution (0.2 g of phosphotungstic acid is dissolved in 5 ml of deionized water) prepared in advance, stirring in an oil bath at 80 ℃ for 12 h, then placing in a water bath at 100 ℃, stirring and evaporating to dryness, drying in an oven at 100 ℃ for 6 h, and roasting in a muffle furnace at 200 ℃ for 4 h to obtain a phosphotungstic acid supported catalyst PW, wherein the PW is marked as 0.2-0.3AD/1 aEVM.
Example 12
The preparation method of the catalyst with the phosphotungstic acid loading of 0.4g comprises the following steps: the amount of phosphotungstic acid used was 0.4g, and the other steps were as described in example 11 and labeled PW0.4-0.3AD/1 aEVM.
Example 13
The preparation method of the catalyst with the phosphotungstic acid loading of 0.6 g comprises the following steps: the amount of phosphotungstic acid used was 0.6 g, and the other steps were as described in example 11 and labeled PW0.6-0.3AD/1 aEVM.
Example 14
The preparation method of the catalyst with the phosphotungstic acid loading of 0.8 g comprises the following steps: the amount of phosphotungstic acid used was 0.8 g, and the other steps were as described in example 11 and labeled PW0.8-0.3AD/1 aEVM.
Examples 15 to 18
Experiment of influence of different phosphotungstic acid loading amounts on catalyst activity: the catalytic activity of the catalysts with different phosphotungstic acid loads prepared in examples 11 to 14 on the dehydration reaction of cyclohexanol was evaluated by the following method.
Putting 0.6 g of the prepared catalyst into a single-neck flask with a fractionating column and a thermometer, adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃ for reaction, collecting a distillate, separating a water layer, removing a plurality of layers of water by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by atmospheric distillation to obtain a colorless and transparent cyclohexene product with pungent smell, wherein the specific cyclohexene yield is shown in Table 2.
TABLE 2 Effect of different phosphotungstic acid loadings on cyclohexene selectivity and yield
Sample (I) Cyclohexene selectivity (%) Cyclohexene yield (%)
PW0.2-0.3AD/1aEVM 100 77.23
PW0.4-0.3AD/1aEVM 100 86.79
PW0.6-0.3AD/1aEVM 100 93.70
PW0.8-0.3AD/1aEVM 100 85.07
Example 19
Experiment of catalytic activity influence by different catalyst dosages: the catalytic activity of the catalyst for dehydration of cyclohexanol was evaluated by the following methods using 0.4g, 0.6 g, 0.8 g, and 1 g of the catalyst, respectively.
Respectively putting 0.4g, 0.6 g, 0.8 g and 1 g of PW0.6-0.3AD/1aEVM catalyst prepared by the catalyst into a single-neck flask with a fractionating column and a thermometer, then adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃ for reaction, collecting a distillate, separating a water layer, removing a plurality of layers of water by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by normal pressure distillation to obtain colorless and transparent cyclohexene products with pungent smell, wherein the specific cyclohexene yield is shown in Table 3.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
TABLE 3 Effect of different catalyst amounts on cyclohexene Selectivity and yield
Amount of catalyst used (g) Cyclohexene selectivity (%) Cyclohexene yield (%)
0.4 100 90.37
0.6 100 93.70
0.8 100 90.36
1 100 89.97

Claims (6)

1. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst are characterized in that: the catalyst takes vermiculite as a carrier, takes one of sodium hexametaphosphate, sodium phosphate and sodium silicate as a binder, and the phosphotungstic acid is loaded on the carrier to form the solid heteropoly acid catalyst, wherein the loading capacity of the phosphotungstic acid is 20-80%.
2. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst according to claim 1 are characterized in that: the carrier vermiculite is high-temperature roasted expanded vermiculite (200-1000 ℃), and the Cation Exchange Capacity (CEC) of the carrier vermiculite is 0.998 mmol/g.
3. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst according to claim 1 are characterized in that: before use, the cation exchange modification treatment is carried out by using 2 mol/L sulfuric acid.
4. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst according to claim 1 are characterized in that: the preparation method of the vermiculite supported phosphotungstic acid green catalyst comprises the following steps:
(1) dissolving 0.1-0.5 g of binder in 2 mol/L of one of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and oxalic acid, wherein the dosage of the binder is 10 ml, and then stirring for 10 min at room temperature by magnetic force until the binder is completely dissolved;
(2) adding 1 g of the high-temperature roasted modified vermiculite powder as shown in the claim 2 into the acid solution obtained in the step (1), and stirring for 1 hour at room temperature to uniformly mix the powder;
(3) dissolving 0.2-0.8 g of phosphotungstic acid in 5 ml of deionized water, adding the mixture obtained in the step (2) after complete dissolution, and stirring in an oil bath at 80 ℃ for 12 hours;
(4) stirring the mixed solution obtained in the step (3) in a water bath at 100 ℃ and evaporating to dryness, and then drying in an oven at 100 ℃ for 6 hours;
(5) and (4) roasting the powder obtained in the step (4) in a muffle furnace at 200 ℃ for 4 h to obtain the phosphotungstic acid supported catalyst.
5. The preparation and application of the vermiculite supported phosphotungstic acid green catalyst according to claim 4 are characterized in that: the high-temperature roasted vermiculite used in the step (2) is 80 meshes and is produced in Yuli county in Xinjiang.
6. The preparation and the application of the vermiculite supported phosphotungstic acid green catalyst according to claim 4 comprise the following steps: placing 0.4-1 g of the catalyst prepared in the claim 4 into a single-neck flask with a fractionating column and a thermometer, adding 10 ml of cyclohexanol, stirring uniformly at room temperature, stirring in an oil bath at 180 ℃, collecting a distillate, separating a water layer, removing water in an organic layer by using anhydrous calcium chloride, and collecting fractions at 80-85 ℃ by atmospheric distillation to obtain a colorless and transparent cyclohexene product with pungent smell.
CN201910779525.2A 2019-08-22 2019-08-22 Preparation and application of vermiculite supported phosphotungstic acid green catalyst Pending CN112403520A (en)

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CN115232361A (en) * 2022-07-13 2022-10-25 塔里木大学 Vermiculite infrared barrier material and preparation method and application thereof

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